Professional Documents
Culture Documents
Coatings 08 00402
Coatings 08 00402
Review
Sputtering Physical Vapour Deposition (PVD) Coatings:
A Critical Review on Process Improvement and Market
Trend Demands
Andresa Baptista 1,2, * , Francisco Silva 2 , Jacobo Porteiro 1 , José Míguez 1 and
Gustavo Pinto 1,2
1 School of Industrial Engineering, University of Vigo, Lagoas, 36310-E Marcosende, Spain;
porteiro@uvigo.es (J.P.); jmiguez@uvigo.es (J.M.); gflp@isep.ipp.pt (G.P.)
2 School of Engineering, Polytechnic of Porto (ISEP), 4200-072 Porto, Portugal; fgs@isep.ipp.pt
* Correspondence: absa@isep.ipp.pt; Tel.: +351-228-340-500
Received: 15 September 2018; Accepted: 2 November 2018; Published: 14 November 2018
Abstract: Physical vapour deposition (PVD) is a well-known technology that is widely used for the
deposition of thin films regarding many demands, namely tribological behaviour improvement,
optical enhancement, visual/esthetic upgrading, and many other fields, with a wide range of
applications already being perfectly established. Machining tools are, probably, one of the most
common applications of this deposition technique, sometimes used together with chemical vapour
deposition (CVD) in order to increase their lifespan, decreasing friction, and improving thermal
properties. However, the CVD process is carried out at higher temperatures, inducing higher stresses
in the coatings and substrate, being used essentially only when the required coating needs to be
deposited using this process. In order to improve this technique, several studies have been carried
out optimizing the PVD technique by increasing plasma ionization, decreasing dark areas (zones
where there is no deposition into the reactor), improving targets use, enhancing atomic bombardment
efficiency, or even increasing the deposition rate and optimizing the selection of gases. These studies
reveal a huge potential in changing parameters to improve thin film quality, increasing as well
the adhesion to the substrate. However, the process of improving energy efficiency regarding the
industrial context has not been studied as deeply as required. This study aims to proceed to a review
regarding the improvements already studied in order to optimize the sputtering PVD process, trying
to relate these improvements with the industrial requirements as a function of product development
and market demand.
Keywords: PVD optimization process; PVD technique; sputtering; magnetron sputtering; deposition
improvement; reactors
1. Introduction
The physical vapour deposition (PVD) process has been known for over 100 years, and
plasma-assisted PVD was patented about 80 years ago [1]. The term “physical vapour deposition”
appeared only in the 60s. At that time, the evolution of vacuum coating processes was needed, which
was carried out through the development of well-known technologies, such as sputtering, vacuum,
plasma technology, magnetic fields, gas chemistry, thermal evaporation, bows, and power sources
control, as described in detail in Powell’s book [2].
In the last 30 years, plasma assisted PVD (PAPVD) was divided into several different power
source technologies such as direct current (DC) diode, triode, radio-frequency (RF), pulsed plasma, ion
beam assisted coatings, among others. In the beginning, the process had some difficulties in being
understood at a fundamental level and necessary changes were introduced to provide benefits, such as
excellent adhesion from the coating to the substrate, structure control, and material deposition at low
temperatures [3].
On the other hand, many additional surface treatments have appeared to meet the industrial and
commercial needs, developing the performance of a huge number of products. In the last decades,
the development of PVD deposition technologies has been focused essentially on the coating of tools,
considering the strong evolution of the computer numerical control (CNC) machining processes, since
new machining approaches have arisen [4].
PVD technique is a thin film deposition process in which the coating grows on the substrate atom
by atom. PVD entails the atomization or vaporization of material from a solid source, usually called
target. Thin films usually have layers with thicknesses as thin as some atomic layers to films with
several microns. This process causes a change in the properties of the surface and the transition zone
between the substrate and the deposited material. On the other hand, the properties of the films can
also be affected by the properties of the substrate. The atomic deposition process can be made in a
vacuum, gaseous, plasma, or electrolytic environment. Moreover, the vacuum environment in the
deposition chamber will reduce the gaseous contamination in the deposition process to a very low
level [5].
The last decades showed an evolution of the PVD techniques, aiming to improve coating
characteristics and deposition rates without putting aside initial surface cleaning to remove possible
contaminations [6,7]. This technique has suffered relevant improvements, mainly in carbides and
nanocomposite transition metal nitrides substrates [8–12]. Research has been focused on improving
the characteristics of coatings, although the enhancement of the deposition rate effectiveness regarding
this process has been the main concern of the industry linked to this kind of techniques [13–15].
The most common surface coating methods in a gaseous state regarding the PVD process are
evaporation and sputtering. These techniques allow for particles to be extracted from the target at very
low pressure to be conducted and deposited onto the substrate [16].
The reactor that was used in the evaporation process requires high-vacuum pressure values.
Generally, these characteristics and parameters have lower atomic energy and less adsorption of gases
into the coatings deposition. As a result, a transfer of particles with larger grains leads to a recognized
lesser adhesion of the particles to the substrate, compared with the sputtering technique. During
deposition, some contaminant particles are released from the melted coating material and moved onto
the substrate, thereby reducing the purity of the obtained coatings. Thus, the evaporation process is
usually used for thicker films and coatings with lower surface morphological requirements, although
this technique presents higher deposition rates when compared with the sputtering process.
Therefore, the sputtering process appears as an alternative for applications that require greater
morphological quality of surfaces where roughness, grain size, stoichiometry, and other requirements
are more significant than the deposition rate. Due to the stresses generated during the cooling
process with the decrease in temperature or the melting temperature of the substrate (polymers), the
deposition process presents temperature limitations for certain applications [17–21]. This leads to the
Sputtering process becoming more relevant among PVD deposition techniques without forgetting
the appearance of new techniques based on the sputtering process to meet the continuous increase in
market requirements.
New coating properties, following market and researchers’ requirements, have been developed
with the emergence of new systems based on conventional processes. Even though the deposition
rates that were obtained by the evaporation process are the desired, the truth is that the sputtering
deposition techniques made an unquestionable progress in terms of quality and increase in deposition
rate, responding to industry and researchers demands interested in this area, even serving as interlayer
for further coatings obtained by chemical vapour deposition (CVD) [22].
CVD is another method of deposition under vacuum and is the process of chemically reacting a
volatile compound from a material to be deposited with other gases, in order to produce a non-volatile
Coatings 2018, 8, 402 3 of 22
solid that is deposited onto a substrate. This method is sometimes used as pre-coating with the aim
of increasing the durability of the substrates, decreasing the friction, and improving the thermal
Coatings 2018, 8, x FOR PEER REVIEW
properties—this means that one can combine deposition methods, like layers of PVD and CVD, 3 of 22
in the
same coating [23–26].
thermal properties—this means that one can combine deposition methods, like layers of PVD and
There are also a large number of studies in mathematical modelling and numerical simulation that
CVD, in the same coating [23–26].
contributeThere are also a large number of studies in mathematical modelling and numerical simulation
to the improvement of this process, which may be an advantage over other processes. These
studies have a great impact on the improvement of the reactors characteristics that lead in the future to
that contribute to the improvement of this process, which may be an advantage over other processes.
the costs reduction, as well as in the improvement of the mechanical properties of the films [27–32].
These studies have a great impact on the improvement of the reactors characteristics that lead in the
This work has as main focus the magnetron sputtering technique since its development will be
future to the costs reduction, as well as in the improvement of the mechanical properties of the films
[27–32].
focused on the improvement of these specific reactors in the future.
This work has as main focus the magnetron sputtering technique since its development will be
2. PVD Coatings
focused on the improvement of these specific reactors in the future.
PVD is an excellent vacuum coating process for the improvement of wear and corrosion resistance.
2. PVD Coatings
It is highly required for functional applications, such as tools, decorative pieces, optical enhancement,
PVD is an excellent vacuum coating process for the improvement of wear and corrosion
moulds, dies, and blades. These are just a few examples of a wide range of already well-established
resistance. It is highly required for functional applications, such as tools, decorative pieces, optical
applications [33–35]. The equipment used in this technique requires low maintenance and the process
enhancement, moulds, dies, and blades. These are just a few examples of a wide range of already
is environmentally
well‐established friendly. Benefits
applications of PVD
[33–35]. The coatings
equipment are used
many.in PVD this can providerequires
technique real andlow unique
advantages that add durability and value to products. Deposition techniques have an important role in
maintenance and the process is environmentally friendly. Benefits of PVD coatings are many. PVD
machining processes.
can provide Machining
real and unique tools are probably
advantages onedurability
that add of the mostand exigent applications,
value to which require
products. Deposition
techniques have an important role in machining processes. Machining tools are probably one of the
characteristics, such as hardness at elevated temperatures, high abrasion resistance, chemical stability,
most exigent applications, which require characteristics, such as hardness at elevated temperatures,
toughness, and stiffness [36–45]. In addition, PVD is also able to produce coatings with excellent
high abrasion resistance, chemical stability, toughness, and stiffness [36–45]. In addition, PVD is also
adhesion, homogeneous layers, designed structures, graduated properties, controlled morphology,
able to produce coatings with excellent adhesion, homogeneous layers, designed structures,
high diversity of materials and properties, among others [46–50].
graduated properties, controlled morphology, high diversity of materials and properties, among
PVD processes allow the deposition in mono-layered, multi-layered and multi-graduated coating
others [46–50].
systems, as PVD wellprocesses
as special alloythe
allow composition
deposition and structures. Among
in mono‐layered, other advantages
multi‐layered of this process,
and multi‐graduated
the variation of coating characteristics continuously throughout the film is undoubtedly
coating systems, as well as special alloy composition and structures. Among other advantages of this one of the
most process, the variation of coating characteristics continuously throughout the film is undoubtedly one
important [32,51,52]. Their flexibility and adaptability to market demands led to the development
and the improvement
of the of techniques
most important [32,51,52]. for theflexibility
Their various and
processes and thus
adaptability multiple
to market variants
demands led have arisen,
to the
somedevelopment and the improvement of techniques for the various processes and thus multiple variants
of them presented in Figure 1.
have arisen, some of them presented in Figure 1.
These techniques are constantly evolving and continue to be inspiration sources for many studies.
These
Many books and techniques are constantly
articles spread evolving and on
out the information continue to be inspiration
these variants, making it sources for to
difficult many
quantify
studies. Many books and articles spread out the information on these variants, making it difficult to
all existing techniques. Sputtering (or cathodic spraying) and Evaporation are the most commonly
quantify all existing techniques. Sputtering (or cathodic spraying) and Evaporation are the most
used PVD methods for thin film deposition.
commonly used PVD methods for thin film deposition.
ARC Stirred
E-Beam Random
Inductive Cathodic Arc Deposition
Resistive
Figure
Figure 1. Segmentation
1. Segmentation of of
thethe current physical
current physical vapour
vapour deposition
deposition(PVD)
(PVD)techniques for advanced
techniques for advanced
coatings.
coatings.
Coatings 2018, 8, x FOR PEER REVIEW
Coatings 2018, 8, 402 44 of 22
of 22
2.1. Evaporation and Sputtering Principles
2.1. Evaporation and Sputtering Principles
In PVD techniques, a thermal physical process of releasing or collision transforms the material
In PVD techniques, a thermal physical process of releasing or collision transforms the material
to be deposited—the target—into atomic particles, which are directed to the substrates in conditions
to be deposited—the target—into atomic particles, which are directed to the substrates in conditions
of gaseous plasma in a vacuum environment, generating a physical coating by condensation or the
of gaseous plasma in a vacuum environment, generating a physical coating by condensation or the
accumulation of projected atoms. A higher flexibility in the types of materials to be deposited and a
accumulation of projected
better composition control atoms.
of the A higher flexibility
deposited films are inthe
theresults
types of
of materials to be [21,53,54].
this technique deposited Two
and
aelectrodes
better composition control of the deposited films are the results of this technique [21,53,54].
connected to a high voltage power supply and a vacuum chamber constitute the PVD Two
electrodes connected to a high voltage power supply and a vacuum chamber constitute the PVD
reactors, as seen in Figure 2 [21,53,55].
reactors, as seen in Figure 2 [21,53,55].
Regarding the sputtering process, fine layers of several materials are applied while using the
Regarding the sputtering process, fine layers of several materials are applied while using the
magnetron sputtering process. The raw material for this vacuum coating process takes the form of a
magnetron sputtering process. The raw material for this vacuum coating process takes the form of a
target. A magnetron is placed near the target in sputtering processes. Then, in the vacuum chamber,
target. A magnetron is placed near the target in sputtering processes. Then, in the vacuum chamber,
an inert gas is introduced, which is accelerated by a high voltage being applied between the target
an inert gas is introduced, which is accelerated by a high voltage being applied between the target and
and the substrate in the direction of the magnetron, producing the release of atomic size particles
the substrate in the direction of the magnetron, producing the release of atomic size particles from the
from the target. These particles are projected as a result of the kinetic energy transmitted by gas ions
target. These particles are projected as a result of the kinetic energy transmitted by gas ions whose
whose have reached the target going to the substrate and creating a solid thin film. The technology
have reached the target going to the substrate and creating a solid thin film. The technology allows for
allows for previous contaminations located on the substrate to be cleaned from the surface—this is
previous contaminations
by reversing the voltage located on the
polarity substrate
between the to be cleaned
substrate and from
the the surface—this
target, is by reversing
usually called cathodic
the voltage polarity
cleaning [21]. between the substrate and the target, usually called cathodic cleaning [21].
When considering the technique of e-beam evaporation, this method involves purely physical
When considering the technique of e‐beam evaporation, this method involves purely physical
processes, where the target acts as an evaporation source containing the material to be deposited,
processes, where the target acts as an evaporation source containing the material to be deposited,
which works as a cathode. Note that the system evaporates any material as a function of the e-beam
which works as a cathode. Note that the system evaporates any material as a function of the e‐beam
power. The material is heated at high vapour pressure by bombarding electrons in high vacuum,
power. The material is heated at high vapour pressure by bombarding electrons in high vacuum, and
and the particles
the particles released.
released. Then,
Then, a clashing
a clashing occurs
occurs betweenthe
between theatomic
atomicsize
sizereleased
released particles
particles and
and gas
gas
molecules—inserted into the reactor, with the aim of accelerating the particles, by creating a plasma.
molecules—inserted into the reactor, with the aim of accelerating the particles, by creating a plasma.
This plasma proceeds through the deposition chamber, being stronger in the middle position of the
This plasma proceeds through the deposition chamber, being stronger in the middle position of the
reactor. Successively compressed layers are deposited, increasing the adhesion of the deposited film to
reactor. Successively compressed layers are deposited, increasing the adhesion of the deposited film
the substrate [17–21].
to the substrate [17–21].
(a) (b)
Figure 2. Schematic drawing of two conventional PVD processes: (a) sputtering and (b) evaporating
Figure 2. Schematic drawing of two conventional PVD processes: (a) sputtering and (b) evaporating
using ionized Argon (Ar+) gas.
using ionized Argon (Ar+) gas.
Being a cleaner deposition process, sputtering permits a better film densification, and reduces
Being a cleaner deposition process, sputtering permits a better film densification, and reduces
residual stresses on the substrate as deposition occurs at low or medium temperature [56–58]. Stress
residual stresses on the substrate as deposition occurs at low or medium temperature [56–58]. Stress
and deposition rate are also controlled by power and pressure. The use of targets with larger area
and deposition rate are also controlled by power and pressure. The use of targets with larger area
facilitates
facilitates aa good uniformity,
good allowing
uniformity, the the
allowing control of the
control of thickness by an by
the thickness easyan
adjustment of the process
easy adjustment of the
parameters and deposition time. However, the process may cause some film contamination by the
process parameters and deposition time. However, the process may cause some film contamination
diffusion of evaporated impurities from the source, thus, there are still some limitations in the selection
by the diffusion of evaporated impurities from the source, thus, there are still some limitations in the
of the materials that were used for the coatings due to their melting temperature.
selection of the materials that were used for the coatings due to their melting temperature.
Coatings 2018, 8, 402 5 of 22
Furthermore, this process does not allow an accurate control of film thickness. However, it allows
for high deposition rates without limit of thickness [59]. For better understanding, a comparison
between evaporation and sputtering techniques is summarized in Table 1.
Coatings 2018, 8, x FOR PEER REVIEW 6 of 22
used—chiller—with two sets of water knockout drums: one is used for the vacuum pumps
and chiller—with two sets of water knockout drums: one is used for the vacuum pumps and the other
the other for cooling targets. Equipment unloading and cooling should not damage coatings’
for cooling targets. Equipment unloading and cooling should not damage coatings’ properties.
Coatings 2018, 8, x FOR PEER REVIEW
properties. The need for a cooling system is a drawback because it decreases production6 of 22 rate and
The need for
rises energetic costs. a cooling system is a drawback because it decreases production rate and rises
chiller—with two sets of water knockout drums: one is used for the vacuum pumps and the other
energetic costs.
for cooling targets. Equipment unloading and cooling should not damage coatings’ properties.
The need for a cooling system is a drawback because it decreases production rate and rises
energetic costs.
Figure 3. The processing flow for a classic PVD sputtering process.
Figure 3. The processing flow for a classic PVD sputtering process.
industrial concern is energy consumption to help reduce costs [64]. New policies
A global industrial concern is energy consumption to help reduce costs [64]. New policies are
A global
are expected Figure 3. The processing flow for a classic PVD sputtering process.
expected to drive more innovation, encourage better industry performance, and lead to more energy
to drive more innovation, encourage better industry performance, and lead to more
savings.
energy savings.
A global industrial concern is energy consumption to help reduce costs [64]. New policies are
The CVD process reveals a higher consumption compared to the PVD when considering all of
The CVD process reveals a higher consumption compared to the PVD when considering
expected to drive more innovation, encourage better industry performance, and lead to more energy
the process steps. This has been demonstrated by several studies, such as sustainability assessments
all ofsavings.
the process steps. This has been demonstrated by several studies, such as sustainability
regarding manufacturing processes, energy consumption, and material flows in hard coating
assessments regarding manufacturing processes, energy consumption, and material flows in hard
The CVD process reveals a higher consumption compared to the PVD when considering all of
processes [65,66].
coating processes [65,66].
the process steps. This has been demonstrated by several studies, such as sustainability assessments
A comparative study issued by Gassner et al. [65], revealed a consumption of 112 kWh (process
regarding
A comparative manufacturing
study issued processes, energy
by Gassner et consumption,
al. [65], revealed and amaterial flows of
consumption
cycle time ≈ 5 h; coating thickness ≤ 6 μm) regarding the TiN deposition, using Magnetron Sputtering in 112
hard coating
kWh (process
processes [65,66].
time ≈ 5 h; coating thickness ≤ 6 µm) regarding the TiN deposition, 2using
cycle(MS) technique, which can be compared with the 974 kWh consumed in the TiCN/Al Magnetron
O3 deposition
Sputtering A comparative study issued by Gassner et al. [65], revealed a consumption of 112 kWh (process
using CVD
(MS)technique, (process
technique, which cycle can be time: 18 h 30 min;
compared with coating thickness ≤ 30
the 974 kWh consumed μm).
inPVD process,
the TiCN/Al2 O3
cycle time ≈ 5 h; coating thickness ≤ 6 μm) regarding the TiN deposition, using Magnetron Sputtering
particularly
deposition usingthe CVD sputtering
technique, process, does cycle
(process not require
time: 18 very
h 30high
min;temperatures, such as
coating thickness ≤the high‐ PVD
30 µm).
(MS) technique, which can be compared with the 974 kWh consumed in the TiCN/Al
temperature that was usually developed in the CVD process. Thus, in the CVD technique, the highest 2O3 deposition
process, particularly the sputtering process, does not require very high temperatures, such as the
using CVD
energy technique, (process
consumption is centred cycle time:
in the 18 h 30 min;
heating coating thickness ≤ 30
step, which μm).
is justified since the PVD process,
temperature
high-temperature
particularly that
the was usually
sputtering developed
process, does not in the CVD
require very process.
high Thus, in thesuch
temperatures, CVD as technique,
the high‐ the
parameters range between 750–1150 °C in the CVD case, and in the MS deposition, are usually done
highest energy consumption is centred in the heating step, which is justified
temperature that was usually developed in the CVD process. Thus, in the CVD technique, the highest since the temperature
at lower temperatures, in the range of 350–600 °C. A possible way of reducing energy consumption
◦
parameters
energy
costs is range between
consumption
recovering is 750–1150
the C the
centred heat
residual in inthrough
the CVDheating
heating case,
step, and in the
which MS deposition,
is justified
exchange modules. since aretemperature
the usually
Furthermore, done at
in MS
temperatures, in the range of 350–600 ◦ C. A possible way of reducing energy consumption costs
lowerdeposition processes, three‐quarters of the total energy is usually consumed in the coating step. In
parameters range between 750–1150 °C in the CVD case, and in the MS deposition, are usually done
at lower temperatures, in the range of 350–600 °C. A possible way of reducing energy consumption
is recovering the residual heat through heating exchange modules. Furthermore, in MS deposition
order to increase energy coating efficiency, recycling target materials must be considered. Thus, it is
costs three-quarters
processes, is recovering
possible to conclude the
of
that residual
the heat
total energy
heating, through
and heating
is usually
etching, exchange
consumed
refrigeration in the
have modules.
a coating Furthermore,
In orderin
step. contribution
much lower to MS
increase
to
energydeposition processes, three‐quarters of the total energy is usually consumed in the coating step. In
energy consumption. Figure 4 compares the energy consumption for the PVD (using MS) and CVD
coating efficiency, recycling target materials must be considered. Thus, it is possible to conclude
order to increase energy coating efficiency, recycling target materials must be considered. Thus, it is
during the deposition steps [65].
that heating, etching, and refrigeration have a much lower contribution to energy consumption.
possible to conclude that heating, etching, and refrigeration have a much lower contribution to
Figure 4 compares the energy consumption for the PVD (using MS) and CVD during the deposition
energy consumption. Figure 4 compares the energy consumption for the PVD (using MS) and CVD
Energy consumption PVD vs CVD
stepsduring the deposition steps [65].
[65].
The way to sustainability and energy efficiency needs to be thought as an opportunity in reducing
costs. The investment in terms of quality improvement of the coatings includes an increasing in
adhesion between those and the corresponding substrates, extending their lifespan. This means that
the reactor must be deeply studied in terms of parameters and external devices used to improve the
deposition process. Beyond the solutions above referred, other possible solutions can be based on the
improvement of the cleaning step within the reactor, minimizing the reactor occupation and saving
costs in terms of energy and assistant gases. The reduction of dark areas into the reactor through the
modelling of the plasma region would increase the useful volume of the chamber, contributing to a
more homogeneous thickness of the coating in a large number of coated parts regarding each batch.
Moreover, if the quality of the coatings is improved regarding its function, the lifespan of the coating
will be enlarged, contributing by this way to energy savings, thus increasing its sustainability.
Figure 5. Characteristics and parameters chambers.
Figure 5. Characteristics and parameters chambers.
Coatings 2018, 8, 402 9 of 22
It is essential to highlight the importance of the useful diameter of the vacuum chambers, because
this parameter will limit the working pressures, and, consequently, the substrates size. The chamber
diameter can vary between 400 and 850 mm [74–77] but it can reach up to 2500 mm under customer
request [74]. Cycle time is relatively fast, for example for a deposition of 3 µm, usually, takes between
5–6 h. Regarding the number of satellites, this can reach twenty, being more common the use of six or
ten satellites.
The rotation systems of the substrates are very important in an industrial context. Its efficiency can
reduce costs and improve film properties, with the rotation speed being determinant in the deposition
sequence of the layer. Studies have shown that this effect is reflected in the morphologic properties of
the coated substrates [60,71,78].
As described in Section 1, in the last years, new pulsed techniques with many potentialities
have emerged. The technique with the greatest impact on its development, taking into account all
sputtering techniques, is undoubtedly the one using Magnetron. However, it can also be used Diode,
Triode, Ion Beam, and Reactive Sputtering systems. The studies on the evolution of the sputtering
magnetron technique in DC and RF contribute to the emergence of techniques, such as dual magnetron
sputtering (DMS), reactive bipolar pulsed dual magnetron sputtering (BPDMS), modulated pulsed
power magnetron sputtering (MPPMS), HiPIMS, dual anode sputtering (DAS), among others.
One of the cheaper power supplies with easy process control is the DC power supply and hence
is the most used although the sputter yield is generally much lower [79]. This makes the DC power
source the most used in magnetron or pulsed systems. Its major disadvantage is the low rate of
ionization. Studies show that only about a fraction of 1% of the target species is sprayed ionized [17].
The DC source only applies when the targets are made of conductive materials. On the other hand, the
RF source is only applicable to the use of non-conductive or low conductivity targets. An alternative to
using DC and RF sources is the Mid Frequency source (MF). To maintain the plasma in the sputtering
process, an alternating high-frequency signal is applied, which allows the current to pass through the
target, thus avoiding the accumulation of charges.
The dual magnetron sputtering (DMS) process uses MF power supply and it has been widely
used for reactive deposition. It has become increasingly sophisticated, being usually used in systems
for industrial applications using magnetron rotation [80,81]. In particular, this method is characterized
by a different composition of the targets and way as the film grows. Surface oxidation is one of the
sensitive aspects of this technique. To counter oxidation, it is necessary to take into account parameters,
such as reactive gas partial pressure, voltage, and sputter rate [80]. Furthermore, in order to receive
DC power and apply pulsed-DC power sources in the magnetrons, components need to be configured
to switch power. This is possible while using a pulsed power supply [80].
DAS is a technology that allows switching from the commonly used alternating current—mid
frequency (AC-MF) mode to a DC power process to reduce the heat load on the substrate.
The BPDMS technique is followed by the DMS technique. The interesting fact about this technique
is that it also uses an MF source like DAS. Rizzo et al. [82] used in their study an MF band of 80–350 kHz.
Using this technique, it was possible to prevent arc formation and its results showed a high deposition
rate of around 0.044 µm min−1 using ZrN coating.
The deposition rate is always the focus of improvement when one thinks to upgrade a reactor
for industrial purposes. The need of the industry thus obliges it, and, in that sense, in the last years,
studies have been conducted also following industrial needs. Some recent investigations have been
focused on the increase of spray ionization, on process stability, on new segmented targets, on gas
flow optimization of different gases, on the bias influence, on obtaining better absorbers, among
others. However, in order to obtain low-cost absorbers as compared to industrial techniques, a
laboratory-tested sputtering unit was tested and the results pointed out that the deposition rates
were low [83]. On the other hand, in studies regarding the gas flow in sprayed zirconia coatings on
flat substrates, the deposition rate results reached 20 µm h−1 , which represents a good deposition
rate. Other studies regarding the influence of bias voltage and gas flow showed that the temperature
Coatings 2018, 8, 402 10 of 22
increase in the substrate and the application of a bias voltage resulted in a decreased deposition rate.
For example, having a substrate temperature of 650 ◦ C and applying a bias voltage at −10 V, it is
possible to obtain a deposition rate of 20 µm h−1 . However, the deposition rate is reduced to 5 µm h−1
if −20 V bias voltage is applied [84,85].
Another approach in an industrial context using the reactor CemeCon® CC800/9 is the study
of Weirather et al. [86]. They used the Reactive Pulsed DC magnetron sputtering technique with
triangle-like segmented targets. That work contributed to show the potential of this technique in an
industrial context, reducing the costs in thin film deposition. Cr1−x Alx N (0.21 ≤ x ≤ 0.74) was used
as a coating material, having obtained low friction values of 0.4 and wear coefficients up to 1.8 ×
10−16 m3 N m−1 , in order to obtain good results regarding the tribological properties. The maximum
hardness obtained was 25.2 GPa, which proved to be a good result.
A study carried out regarding the plastics industry compared conventional DC, MF pulsed and
HiPIMS techniques considering the deposition rate and coating’s hardness. It is noteworthy that the
complex geometry of the injection moulding tools was an additional challenge in this study, taking into
account the three technologies that were used. For the three different technologies, five different targets
configurations were used, varying the chemical composition of the (Cr1−x Alx )N coatings. The HiPIMS
technique provided the best results for aluminium deposition rate, which was reflected in an increase
from 1.32 to 1.67 µm h−1 . In this case, the deposition rates of DC and MF coatings decrease from about
2.45 to 1.30 µm h−1 . On the other hand, chromium deposition rate presented the worst results for the
HiPIMS technique as compared to DC and MF ones. The morphology, surface, and roughness that
were obtained by the HiPIMS technique showed almost constant coatings behaviour [87].
HiPIMS technology allows for combining technologies, such as cathodic arc plasma deposition
and ion plating, with this being its greatest advantage [88]. Although this type of reactor appeared in
the 1990s, with the evolution of sputtering magnetron technology, just in recent years it has known
more interest in its improvement and in exploring its potentialities. Since then, it has been used
in the improvement of the spray ionization through the pulsed power that influences the plasma
conditions and the coating’s properties. When compared to conventional magnetron sputtering, the
studies about this technique have shown significant improvements in coating structure, properties,
and adhesion [89,90]. On the other hand, the combination of HiPIMS and DC-Pulsed also shows
evidence in improving adhesion and morphology while using TiSiN coating [91]. Although versatile,
it is necessary to have some care in the process and in the evaluation of results, given the difficulty in
obtaining consistent and repeatable results [92].
One variation of the HiPIMS is the power pulses method MPPMS. This technique uses a pulsed
high peak target power density for a short period of time and creates high-density plasma with an
elevated degree of ionization of the sputtered species [93].
Deep oscillation magnetron sputtering (DOMS) is another variant of HiPIMS. A study that was
carried out using this system led to seeking a relation between the ionization of the sputtered species
and thin film properties [94]. This investigation had the purpose of identifying the mechanisms
which influence the shadowing effect in this technique. To effectively reduce the atomic shadows, it
was necessary to accelerate the chromium ions in the substrate sheath in the DOMS, which reduces
significantly the high angle component of its collision. A high degree of ionization allows the deposition
of dense and compact films without the need for the bombardment of high-energy particles during the
coating growing process.
Plasma enhanced magnetron sputtering (PEMS) is an advanced version of conventional DC
magnetron sputtering (DCMS). In conventional MS, the discharge plasma is generated in front of
the magnetrons, as can be seen in Figure 6a. On the other hand, PEMS assisted deposition has the
advantage of generating an independent plasma through impact ionization by accelerating electrons
that are emitted from hot filaments in the chamber, which expands through the entire vacuum chamber,
as shown in the illustration of Figure 6b. Lin et al. [95] carried out a comparative study between
the techniques DCMS and HiPIMS with and without PEMS assistance regarding the deposition of
Coatings 2018, 8, 402 11 of 22
Coatings 2018, 8, x FOR PEER REVIEW 11 of 22
TiSiCN nanocomposite coatings, concluding that PEMS assistance improves the microstructure and
mechanical properties of coatings that are produced by DOMS or DCMS, as well as the reduction of
mechanical properties of coatings that are produced by DOMS or DCMS, as well as the reduction of
residual stress.
residual stress.
Figure
Figure 6.
6. Schematic
Schematiccomparison
comparisonbetween
between(a) (a)
conventional magnetron sputtering
conventional magnetron (MS), and
sputtering (MS), andthe the
(b)
plasma enhanced magnetron sputtering (PEMS) assisted process. Reproduced from [95] with permission.
(b) plasma enhanced magnetron sputtering (PEMS) assisted process. Reproduced from [95] with
Copyright 2018 Elsevier.
permission. Copyright 2018 Elsevier.
The receptivity of the industry to the HiPIMS technique has been very positive bearing in mind
The receptivity of the industry to the HiPIMS technique has been very positive bearing in mind
the range
the range ofof
reactor power
reactor supply.
power Emerging
supply. technologies
Emerging allow gains
technologies allow around the 30% in
gains around the
the ionization
30% in the
rate and higher charge states of the target ions. This high degree of ionization results in increased
ionization rate and higher charge states of the target ions. This high degree of ionization results in
advantages of some coating properties, such as improved adhesion and the possibility of consistently
increased advantages of some coating properties, such as improved adhesion and the possibility of
covering surfaces
consistently withsurfaces
covering complexwith
geometry [79,96].
complex Thus, [79,96].
geometry the scientific
Thus, community hascommunity
the scientific focused on has
the
development of high power magnetic pulsed technologies, since these results are very interesting
focused on the development of high power magnetic pulsed technologies, since these results are very
concerning the industrial context.
interesting concerning the industrial context.
(a)
(a) (b)
(b)
Figure 7. Vacuum system setup using (a) external unbalanced magnetic field, (b) external electric and
Figure 7. Vacuum system setup using (a) external unbalanced magnetic field, (b) external electric and
Figure 7. Vacuum system setup using (a) external unbalanced magnetic field, (b) external electric and
magnetic fields, with the auxiliary anode. (a) Reproduced from [97] with permission. Copyright 2016
magnetic fields, with the auxiliary anode. (a) Reproduced from [97] with permission. Copyright 2016
magnetic fields, with the auxiliary anode. (a) Reproduced from [97] with permission. Copyright 2016
Elsevier. (b) Reproduced from [98] with permission. Copyright 2017 Elsevier.
Elsevier. (b) Reproduced from [98] with permission. Copyright 2017 Elsevier.
Elsevier. (b) Reproduced from [98] with permission. Copyright 2017 Elsevier.
Other
Other examples using an auxiliary
Other examples using
examples using an auxiliary magnetic
an auxiliary magnetic field
magnetic field as as external
field as external device
external device showed
device showed more more ambitious
showed more ambitious
ambitious
results, presenting increased deposition rates between 40% and 140% when
results, presenting increased deposition rates between 40% and 140% when considering the inclusion
results, presenting increased deposition rates between 40% and 140% when considering the inclusion considering the inclusion
of
of an
of an external
an external device
external device with
device with different
with different
different types types
types of of targets
of targets that
targets that were
that were chosen
were chosen
chosen due due
due to to their
to their relevance
their relevance in
relevance in
in
technological applications. The results were compared with the HiPIMS
technological applications. The results were compared with the HiPIMS process without the external
technological applications. The results were compared with the HiPIMS process without the external process without the external
device under similar experimental conditions (working gas pressure, average power). Figure 8 shows
device under similar experimental conditions (working gas pressure, average power). Figure 8 shows
device under similar experimental conditions (working gas pressure, average power). Figure 8 shows
the configuration of the setup used. However, it is possible to improve the system, as described by the
the configuration of the setup used. However, it is possible to improve the system, as described by
the configuration of the setup used. However, it is possible to improve the system, as described by
researchers
the that are
the researchers
researchers involved
that
that are in that in
are involved
involved work.
in that
that It work.
was
work. shown
It a great
It was
was potential
shown
shown a forpotential
a great
great depositionfor
potential improvement
for deposition
deposition
in HiPIMS through the control of the magnetic field and pulse configuration
improvement in HiPIMS through the control of the magnetic field and pulse configuration [99].
improvement in HiPIMS through the control of the magnetic field and pulse configuration [99]. [99].
Using magnetic fields, Ganesan et al. [100] showed that it is possible to increase the deposition
Using magnetic fields, Ganesan et al. [100] showed that it is possible to increase the deposition
Using magnetic fields, Ganesan et al. [100] showed that it is possible to increase the deposition
rate, guiding the ion flux in the direction of the substrate with the application of an external magnetic
rate, guiding the ion flux in the direction of the substrate with the application of an external magnetic
rate, guiding the ion flux in the direction of the substrate with the application of an external magnetic
field using a solenoidal coil, excited with a DC current pulse. This is the scheme that is used in this
field using a solenoidal coil, excited with a DC current pulse. This is the scheme that is used in this
field using a solenoidal coil, excited with a DC current pulse. This is the scheme that is used in this
study,
study, as
study, as depicted
as depicted
depicted inin
Figure
in 9; it9;
Figure
Figure isit
9; possible
it is to seeto
is possible
possible insee
to the in
see centre
the of
in the the chamber
centre
centre of
of the the additional
the chamber
chamber the solenoidal
the additional
additional
coil that provides an external magnetic field.
solenoidal coil that provides an external magnetic field.
solenoidal coil that provides an external magnetic field.
Figure 8. Schematic drawing of the experimental setup used in the work. Reproduced from [99] with
Figure 8. Schematic drawing of the experimental setup used in the work. Reproduced from [99] with
Figure 8. Schematic drawing of the experimental setup used in the work. Reproduced from [99] with
permission. Copyright 2018 Elsevier.
permission. Copyright 2018 Elsevier.
permission. Copyright 2018 Elsevier.
Coatings 2018, 8, 402 13 of 22
Coatings 2018, 8, x FOR PEER REVIEW 13 of 22
Figure 9. Experimental unit high power impulse magnetron sputtering (HiPIMS) deposition system
Figure 9. Experimental unit high power impulse magnetron sputtering (HiPIMS) deposition system
showing
showing thethe additional
additional solenoidal
solenoidal coil.
coil. Reproduced
Reproducedfrom [100]
from with with
[100] permission. Copyright
permission. 2019
Copyright
Elsevier.
2019 Elsevier.
TheThe study
study shows
shows evidence of
evidence of intensification
intensification in
in the
the ionization
ionizationzone
zonethat
thatincreases
increasesthe plasma
the plasma
extension and density, leading to an increase in the deposition rate through
extension and density, leading to an increase in the deposition rate through the combination the combination of of
magnetic and reactor magnetron fields. This evidence can be interpreted in
magnetic and reactor magnetron fields. This evidence can be interpreted in Figure 10, where (a)Figure 10, where (a)
represents a conventional situation of deposition by the generation of transporting ions in neutral (N)
represents a conventional situation of deposition by the generation of transporting ions in neutral
and ionized fluxes (I) plasmas, those are deposited on the substrate. The same happens on (b),
(N) and ionized fluxes (I) plasmas, those are deposited on the substrate. The same happens on (b),
although applying the magnetic field. The ionization zone will be extended, activating additional
although applying the magnetic field. The ionization zone will be extended, activating additional ions
ions that will be directed to the substrate, increasing the deposition rate. The results show that an
that will be directed to the substrate, increasing the deposition rate. The results show that an increased
increased maximum peak current and/or in the power density corresponds to a significant
maximum peak current and/or in the power density corresponds to a significant improvement in the
improvement in the pulverized ions flow. It has further been found that an increase of about 25% in
pulverized ions flow. It has further been found that an increase of about 25% in peak current is seen
peak current is seen when a 150 A magnetic field at the start of the HiPIMS pulse is used, inducing a
when a 150 A magnetic field at the start of the HiPIMS pulse is used, inducing a 25% increase in the rate
25% increase in the rate of the target ion emission as compared to the case where no external magnetic
of field is applied [100].
the target ion emission as compared to the case where no external magnetic field is applied [100].
Figure 10. Schematic illustration of a film deposition, (a) without the external device and (b) with the
Figure 10. Schematic illustration of a film deposition, (a) without the external device and (b) with
theapplication of an external magnetic field. Reproduced from [100] with permission. Copyright 2019
application of an external magnetic field. Reproduced from [100] with permission. Copyright
Elsevier.
2019 Elsevier.
Coatings 2018, 8, 402
Coatings 2018, 8, x FOR PEER REVIEW 14 of 22
14 of 22
In order to improve Cu films, Wu et al. [101] studied the utilization of a modified HiPIMS system
In order to improve Cu films, Wu et al. [101] studied the utilization of a modified HiPIMS system
using a positive kick voltage after an initial negative pulse, being possible to control the magnitude
using a positive kick voltage after an initial negative pulse, being possible to control the magnitude
and the pulse width of the reverse pulse. This result is interpreted by a bipolar pulsed effect that was
and the in
studied pulse width
detail of the
in this type reverse pulse. This
of deposition. result
Figure 11 is interpreted
shows by a that
the results bipolar
were pulsed effect
obtained in that
the
was studied in detail in this type of deposition. Figure 11 shows the results that were obtained
deposition of Cu films using three different kick pulses, comparing three different systems: DC
in the deposition
magnetron of Cu(DCMS),
sputtering films using three different
conventional kickand
HiPIMS, pulses, comparing
Bipolar Pulsed. three different
It was found systems:
that the
DC magnetron sputtering (DCMS), conventional HiPIMS, and Bipolar Pulsed. It
increase in the voltage amplitude and pulse width of the kick pulse can promote an increase of the was found that
the increase in the voltage amplitude and pulse width of the kick pulse can promote an increase
deposition rate relatively to the conventional HiPIMS, but even so, the deposition rate that was of
the deposition rate relatively to the conventional HiPIMS, but even so, the deposition rate that was
achieved by the DCMS process showed to be higher. To conclude, the HiPIMS bipolar pulse shows
achieved by the DCMS process showed to be higher. To conclude, the HiPIMS bipolar pulse shows
great potential and this new approach can improve Cu film properties such as electronic conductivity
greatadhesion.
and potential and this new
However, in approach
order to can improve
achieve Cu film rates
deposition properties such
higher as DCMS,
than electronic conductivity
the substrates
and adhesion. However, in order to achieve deposition rates higher than DCMS, the substrates
positioning needs to be planned in the centre of the reactor, where the deposition rate is more
positioning needs to be planned in the centre of the reactor, where the deposition rate is more effective.
effective.
Figure 11. Results relatively to Cu films deposition rate. Average deposition rates for all the samples
Figure 11. Results relatively to Cu films deposition rate. Average deposition rates for all the samples at
at different positions in the reactor. Reproduced from [101] with permission. Copyright 2018 Elsevier.
different positions in the reactor. Reproduced from [101] with permission. Copyright 2018 Elsevier.
The combination of two or more vacuum chambers in improving the process and its efficiency
The combination of two or more vacuum chambers in improving the process and its efficiency
should be
should be considered.
considered. This approach
This cancan
approach be seen in thein recent
be seen work of
the recent Bras of
work et al. [102],
Bras which
et al. simulates
[102], which
an industrial in-line vacuum production of solar cells using as a deposit compound the copper
simulates an industrial in‐line vacuum production of solar cells using as a deposit compound the indium
gallium selenide (CIGS). The use of the sputtering technique in the industrial context applied in the
copper indium gallium selenide (CIGS). The use of the sputtering technique in the industrial context
production of solar cells was demonstrated. In this study, automated arms were used to load and
applied in the production of solar cells was demonstrated. In this study, automated arms were used
unload the cells. The system presents a process sequence using two vacuum chambers and 25 cathodic
to load and unload the cells. The system presents a process sequence using two vacuum chambers
spray25
and stations, which
cathodic hasstations,
spray its own heating
which and
has helium
its own cooling arrangement.
heating and helium Following
cooling the simplified
arrangement.
process in Figure 12, it can be seen: (a) in chamber A sputtering stations 1 to 5, where the substrate
Following the simplified process in Figure 12, it can be seen: (a) in chamber A sputtering stations 1 to
cleaning and absorber metal layers are carried out; (b) in the transition chamber A to B, the heating
5, where the substrate cleaning and absorber metal layers are carried out; (b) in the transition chamber
station increases the substrate temperature to improve deposition; (c) in chamber B, sputtering stations
A to B, the heating station increases the substrate temperature to improve deposition; (c) in chamber
6–18 promote the deposition of CIGS layers and the substrate is then rapidly cooled down in the
B, sputtering stations 6–18 promote the deposition of CIGS layers and the substrate is then rapidly
intermediate chamber, and, finally, back to the chamber A; and, (d) sputtering stations 19–25 are
cooled down in the intermediate chamber, and, finally, back to the chamber A; and, (d) sputtering
producing the buffer layer in an oxygen-containing atmosphere. To finalize the cells, the addition of
stations 19–25 are producing the buffer layer in an oxygen‐containing atmosphere. To finalize the
resistive transparent conductive oxide (TCP) bilayers is needed. The efficiency was demonstrated for
cells, the addition of resistive transparent conductive oxide (TCP) bilayers is needed. The efficiency
cells with a total area of 1 cm2 and 225 cm2 with values
was demonstrated for cells with a total area of 1 cm of 15.1% and
2 and 225 cm 13.2%, respectively.
2 with values of 15.1% and 13.2%,
respectively.
Coatings 2018, 8, 402 15 of 22
Coatings 2018, 8, x FOR PEER REVIEW 15 of 22
(d)
(c)
(a) (b)
Figure 12. The schematic process sequence of the load-lock DUO solar cell manufacturing system
Figure 12. The schematic process sequence of the load‐lock DUO solar cell manufacturing system of
of Midsummer ® , (a) stations 1 to 5, (b) heating station, (c) stations 6 to 18 and (d) stations 19 to 25.
Midsummer ®, (a) stations 1 to 5, (b) heating station, (c) stations 6 to 18 and (d) stations 19 to 25.
Reproduced from [102] with permission. Copyright 2017 Elsevier.
Reproduced from [102] with permission. Copyright 2017 Elsevier.
Kapopara et al. [29,30], predicted the gases concentration and distribution (argon and nitrogen),
density profiles, velocity profiles, and pressure profiles across the sputtering chamber. They conclude
that the locations of both gas inlet port and substrate have a crucial influence on the gas distribution
inside the chamber. With this study, it was possible to propose a modification of the reactor geometry
for a better gas flow over the substrate. This research showed that the CFD simulation has a great
potential and its influence is growing over the time on the PVD reactors studies. After the modulation
phase, it allows varying parameters, being a strong advantage in an industrial context due to the
capacity of predicting the final results regarding the different phenomena that occur in the reactor
during the deposition process. The main goal is a reduction in the production time, with a consequent
reduction in costs, maintaining the quality standards.
Trieschmann [115] also used the DSMC to study neutral gas simulation on the influence of rotating
spokes on gas rarefaction in HiPIMS. This different approach helps to understand the gas dynamics in
the harsh discharge condition. It was concluded that the influence of a rotating plasma ionization zone
is limited by a segmented time-modulated sputtering inlet distribution [115].
To conclude, the CFD modelling has been carried out to analyze gas flow and its mixing behaviour
within the chamber reactor. However, for a better approximation of a real situation, it is important
to use different models and compare them. The models defined and studied are important on the
advance of geometry and parameters changes in the reactors that can be simulated, also taking into
account external devices, in order to improve the process.
4. Concluding Remarks
PVD techniques are in constant evolution, accompanying the appearance of new technologies
that are being adapted to the processes. They also meet the increasing demands of the industry.
Furthermore, the focus of researchers in the last years has been on improving reactors and the
application of external devices to the detriment of improving the properties of films, which has
passed to the background, following the needs of industry.
Optimizing energy consumption of PVD processes is an opportunity for improvement. It is in the
deposition step that this improvement can be reflected, since it is in this step of the process that PVD
shows greater consumption. In the CVD process, it represents 33.5%, whereas in the PVD process, it
represents 77.7% of consumption.
New opportunities in the development of techniques have contributed to the appearance of the
MF power source that allowed the combination of DC and RF sources. The DC sources remain the
most used type while the RF source is the least used. However, the combination of the sources in the
DAS technique allowed for reducing the heat load on the substrate, thus improving the film properties,
giving to this technique a huge yield for improvement.
External devices have emerged as a result of the PVD techniques enhancement. The HiPIMS
method shows evidence of this application and improvement for high-performance thin films.
This technology has had a good acceptance by the industry, which contributed to accelerating the
researcher’s interest. In addition, the good results obtained with the application of external devices
has shown an increase in deposition rates due to plasma intensification. The coatings industry has
evolved to the HiPIMS reactors due to the facts above-mentioned, and it is believable that this trend
remains in the same way in the near future.
With technology evolution, simulations are currently a reality. Softwares, such as FEM and CFD,
support this evolution in reducing production costs and adapting external devices. In addition, they
respond to solve complex engineering problems in an industrial context. However, the use of CFD in
solving coating problems can still grow in the light of its potential. New developments are expected as
technology and software advances in deposition systems.
Coatings 2018, 8, 402 17 of 22
Author Contributions: Conceptualization, A.B. and F.S.; Methodology, A.B. and F.S.; Writing-Original Draft
Preparation, A.B.; Writing-Review & Editing, F.S. and G.P.; Supervision, J.P., J.M. and F.S.
Funding: This research received no external funding.
Acknowledgments: Authors Andresa Baptista and Gustavo Pinto thank the support of CIDEM/ISEP.
Conflicts of Interest: The authors declare no conflict of interest.
Nomenclature
AC-MF Alternating Current—Mid Frequency
BPDMS Reactive Bipolar Pulsed Dual MS
CFD Computational Fluid Dynamics
CIGS Copper Indium Gallium Selenide
CNC Computer numerical control
CVD Chemical Vapour Deposition
DAS Dual Anode Sputtering
DC Direct Current
DCMS Direct Current Magnetron Sputtering
DMS Dual Magnetron Sputtering
DSMC Direct Simulation Monte Carlo
E-Beam Electron Beam Gun
FEM Finite Elements Methods
HiPIMS High Power Impulse Magnetron Sputtering
HPPMS High-Power Pulsed Magnetron Sputtering
MEP Magnetically Enhanced Plasma
MF Mid Frequency
MPPMS Modulated Pulsed Power MS
MS Magnetron Sputtering
PAPVD PVD Plasma Assisted
PEMS Plasma enhanced magnetron sputtering
PVD Physical Vapour Deposition
RF Radio Frequency
TCP Transparent Conductive Oxide
UBMS Unbalanced Magnetron Sputtering
References
1. Berghaus, B. Improvements in and Related to the Coating of Articles by Means of Thermally Vapourized
Material. UK Patent 510992, 1938.
2. Powell, C.F.; Oxley, J.H.; Blocher, J.M. Vapour Deposition; John Wiley & Sons: New York, NY, USA, 1966.
3. Holmberg, K.; Matthews, A. Coatings Tribology: Properties, Techniques and Applications in Surface Engineering;
Elsevier Science: Amsterdam, The Netherlands, 1994; p. 440.
4. Tracton, A.A. Coatings Technology: Fundamentals, Testing, and Processing Techniques; CRC Press: Boca Raton,
FL, USA, 2007; pp. 238–284.
5. Mattox, D.M. Handbook of Physical Vapor Deposition (PVD) Processing Film Formation, Adhesion, Surface
Preparation and Contamination Control; Knovel: Norwich, NY, USA, 1998.
6. Silva, F.J.G.; Neto, M.A.; Fernandes, A.J.S.; Costa, F.M.; Oliveira, F.J.; Silva, R.F. Adhesion and wear behaviour
of NCD coatings on Si3 N4 by micro-abrasion tests. J. Nanosci. Nanotechnol. 2009, 9, 3938–3943. [CrossRef]
[PubMed]
7. Martinho, R.P.; Silva, F.J.G.; Alexandre, R.J.D.; Baptista, A.P.M. TiB2 Nanostructured coating for GFRP
injection moulds. J. Nanosci. Nanotechnol. 2011, 11, 5374–5382. [CrossRef] [PubMed]
8. Musil, J. Flexible hard nanocomposite coatings. RSC Adv. 2015, 5, 60482–60495. [CrossRef]
9. Veprek, S.; Veprek-Heijman, M.G.J.; Karvankova, P.; Prochazka, J. Different approaches to super hard coatings
and nanocomposites. Thin Solid Films 2005, 476, 1–29. [CrossRef]
Coatings 2018, 8, 402 18 of 22
10. Yang, Q.; Zhao, L.R. Microstructure, mechanical and tribological properties of novel multi-component
nanolayered nitride coatings. Surf. Coat. Technol. 2005, 200, 1709–1713. [CrossRef]
11. Martinho, R.P.; Andrade, M.F.C.; Silva, F.J.G.; Alexandre, R.J.D.; Baptista, A.P.M. Microabrasion wear
behaviour of TiAlCrSiN nanostructured coatings. Wear 2009, 267, 1160–1165. [CrossRef]
12. Silva, F.J.G.; Martinho, R.P.; Baptista, A.P.M. Characterization of laboratory and industrial
CrN/CrCN/diamond-like carbon coatings. Thin Solid Films 2014, 550, 278–284. [CrossRef]
13. Rubshtein, A.P.; Vladimirov, A.B.; Korkh, Y.V.; Ponosov, Y.S.; Plotnikov, S.A. The composition, structure and
surface properties of the titanium-carbon coatings prepared by PVD technique. Surf. Coat. Technol. 2017, 309,
680–686. [CrossRef]
14. Silva, F.J.G.; Martinho, R.P.; Alexandre, R.; Baptista, A.M. Wear resistance of TiAlSiN thin coatings. J. Nanosci.
Nanotechnol. 2012, 12, 9094–9101. [CrossRef] [PubMed]
15. Sam, Z. Thin Films and Coatings: Toughening and Toughness Characterization, 1st ed.; CRC Press: Boca Raton,
FL, USA, 2015; pp. 377–463.
16. Mubarak, A.M.A.; Hamzah, E.H.E.; Tofr, M.T.M. Review of Physical Vapour Deposition (PVD) Techniques
for Hard Coating. Jurnal Mekanikal 2005, 20, 42–51.
17. Mattox, D.M. Handbook of Physical Vapor Deposition (PVD) Processing; William Andrew: Amsterdam, The
Netherlands, 2010; p. 792.
18. Holmberg, K.; Matthews, A. Coatings Tribology: Properties, Mechanisms, Techniques and Applications in Surface
Engineering, 2nd ed.; Elsevier: Amsterdam, The Netherlands, 2009; p. 576.
19. Tracton, A.A. Coatings Technology Handbook, 3rd ed.; CRC Press: Boca Raton, FL, USA, 2006.
20. Martin, P.M. Handbook of Deposition Technologies for Films and Coatings, 3rd ed.; Elsevier: Amsterdam, The
Netherlands, 2010.
21. Mattox, D.M. The Foundations of Vacuum Coating Technology; Noyes Publications: Norwich, UK, 2003.
22. Silva, F.J.G.; Baptista, A.P.M.; Pereira, E.; Teixeira, V.; Fan, Q.H.; Fernandes, A.J.S.; Costa, F.M. Microwave
plasma chemical vapour deposition diamond nucleation on ferrous substrates with Ti and Cr interlayers.
Diam. Relat. Mater. 2002, 11, 1617–1622. [CrossRef]
23. Silva, F.J.G. Nanoindentation on Tribological Coatings. In Applied Nanoindentation in Advanced Materials;
Tiwari, A., Natarajan, S., Eds.; Wiley: New York, NY, USA, 2017; pp. 111–133.
24. Silva, F.J.G.; Fernandes, A.J.S.; Costa, F.M.; Teixeira, V.; Baptista, A.P.M.; Pereira, E. Tribological behavior of
CVD diamond films on steel substrates. Wear 2003, 255, 846–853. [CrossRef]
25. Damm, D.D.; Contin, A.; Barbieri, F.C.; Trava-Airoldi, V.J.; Barquete, D.M.; Corat, E.J. Interlayers applied to
CVD diamond deposition on steel substrate: A review. Coatings 2017, 7, 141. [CrossRef]
26. Trucchi, D.M.; Bellucci, A.; Girolami, M.; Mastellone, M.; Orlando, S. Surface texturing of CVD diamond
assisted by ultra short laser pulses. Coating 2017, 7, 185. [CrossRef]
27. Voottipruex, P.; Bergado, D.T.; Lam, L.G.; Hino, T. Back-analyses of flow parameters of PVD improved soft
Bangkok clay with and without vacuum preloading from settlement data and numerical simulations. Geotext.
Geomembr. 2014, 42, 457–467. [CrossRef]
28. Bobzin, K.; Brinkmann, R.; Mussenbrock, T.; Bagcivan, N.; Brugnara, R.; Schäfer, M.; Trieschmann, J.
Continuum and kinetic simulations of the neutral gas flow in an industrial physical vapor deposition reactor.
Surf. Coat. Technol. 2013, 237, 176–181. [CrossRef]
29. Kapopara, J.; Mengar, A.; Chauhan, K.; Rawal, S. CFD Analysis of Sputtered TiN Coating. Mater. Today Proc.
2017, 4, 9390–9393. [CrossRef]
30. Kapopara, J.M.; Mengar, A.R.; Chauhan, K.V.; Patel, N.P.; Rawal, S.K. Modelling and analysis of sputter
deposited ZrN coating by CFD. In Proceedings of the IConAMMA 2016 International Conference on
Advances in Materials and Manufacturing Applications, Bangalore, India, 14–16 July 2016; p. 012205.
31. Skordaris, G.; Bouzakis, K.; Kotsanis, T.; Charalampous, P.; Bouzakis, E.; Breidenstein, B.; Bergmann, B.;
Denkena, B. Effect of PVD film’s residual stresses on their mechanical properties, brittleness, adhesion and
cutting performance of coated tools. CIRP J. Manuf. Sci. Technol. 2017, 18, 145–151. [CrossRef]
32. Skordaris, G.; Bouzakis, K.; Kotsanis, T.; Charalampous, P.; Bouzakis, E.; Lemmer, O.; Bolz, S. Film thickness
effect on mechanical properties and milling performance of nano-structured multilayer PVD coated tools.
Surf. Coat. Technol. 2016, 307, 452–460. [CrossRef]
Coatings 2018, 8, 402 19 of 22
33. Fox-Rabinovich, G.; Paiva, J.M.; Gershman, I.; Aramesh, M.; Cavelli, D.; Yamamoto, K.; Dosbaeva, G.;
Veldhuis, S. Control of self-organized criticality through adaptivebehavior of nano-structured thin film
coatings. Entropy 2016, 18, 290. [CrossRef]
34. Hoche, H.; Groß, S.; Oechsner, M. Development of new PVD coatings for magnesium alloys with improved
corrosion properties. Surf. Coat. Technol. 2014, 259, 102–108. [CrossRef]
35. Korhonena, H.; Syväluoto, A.; Leskinen, J.T.T.; Lappalainen, R. Optically transparent and durable Al2 O3
coatings for harsh environments by ultra short pulsed laser deposition. Opt. Laser Technol. 2018, 98, 373–384.
[CrossRef]
36. Inspektor, A.; Salvador, P.A. Architecture of PVD coatings for metalcutting applications: A review. Surf. Coat.
Technol. 2014, 257, 138–153. [CrossRef]
37. Momeni, S.; Tillmann, W. Investigation of these lf-healing sliding wear characteristics of NiTi-based PVD
coatings on tool steel. Wear 2016, 368, 53–59. [CrossRef]
38. Michailidis, N. Variations in the cutting performance of PVD-coated tools in milling Ti6Al4V, explained
through temperature-dependent coating properties. Surf. Coat. Technol. 2016, 304, 325–329. [CrossRef]
39. Gouveia, R.M.; Silva, F.J.G.; Reis, P.; Baptista, A.P.M. Machining duplex stainless steel: Comparative study
regarding end mill coated tools. Coatings 2016, 6, 51. [CrossRef]
40. Martinho, R.P.; Silva, F.J.G.; Baptista, A.P.M. Cutting forces and wear analysis of Si3N4 diamond coated tools
in high speed machining. Vacuum 2008, 82, 1415–1420. [CrossRef]
41. Nunes, V.; Silva, F.J.G.; Andrade, M.F.; Alexandre, R.; Baptista, A.P.M. Increasing the lifespan of high-pressure
die cast molds subjected to severe wear. Surf. Coat. Technol. 2017, 332, 319–331. [CrossRef]
42. Fernandes, L.; Silva, F.J.G.; Andrade, M.F.; Alexandre, R.; Baptista, A.P.M.; Rodrigues, C. Increasing the
stamping tools lifespan by using Mo and B4C PVD coatings. Surf. Coat. Technol. 2017, 325, 107–119.
[CrossRef]
43. Vereschaka, A.; Kataeva, E.; Sitnikov, N.; Aksenenko, A.; Oganyan, G.; Sotova, C. Influence of Thickness of
Multilayered Nano-Structured Coatings Ti-TiN-(TiCrAl)N and Zr-ZrN-(ZrCrNbAl)N on Tool Life of Metal
Cutting Tools at Various Cutting Speeds. Coatings 2018, 8, 44. [CrossRef]
44. Baptista, A.; Silva, F.J.G.; Pinto, G.; Porteiro, J.; Míguez, J.; Fernandes, L. On the physical vapour deposition
(PVD) process evolution. Procedia Manuf. 2018, in press.
45. Pinto, G.; Silva, F.J.G.; Baptista, A.; Porteiro, J.; Míguez, J.; Fernandes, L. A critical review on the numerical
simulation related to physical vapour deposition. Procedia Manuf. 2018, in press.
46. Maity, S. Optimization of processing parameters of in-situ polymerization of pyrrole on woollen textile to
improve its thermal conductivity. Prog. Org. Coat. 2017, 107, 48–53. [CrossRef]
47. Kim, M.; Kim, S.; Kim, T.; Lee, D.K.; Seo, B.K.; Lim, C.S. Mechanical and thermal properties of epoxy
composites containing zirconium oxide impregnated halloysite nanotubes. Coatings 2017, 7, 231. [CrossRef]
48. Hu, N.; Khan, M.; Wang, Y.; Song, X.; Lin, C.; Chang, C.; Zeng, Y. Effect of Microstructure on the Thermal
Conductivity of Plasma Sprayed Y2 O3 Stabilized Zirconia (8% YSZ). Coatings 2017, 7, 198. [CrossRef]
49. Silva, F.J.G.; Casais, R.C.B.; Martinho, R.P.A.; Baptista, P.M. Mechanical and tribological characterization of
TiB2 thin films. J. Nanosci. Nanotechnol. 2012, 12, 9187–9194. [CrossRef] [PubMed]
50. Silva, F.J.G.; Martinho, R.P.; Andrade, M.; Baptista, A.P.M.; Alexandre, R. Improving the wear resistance of
moulds for the injection of glass fibre–reinforced plastics using PVD coatings: A comparative study. Coatings
2017, 7, 28. [CrossRef]
51. Abdullah, M.Z.B.; Ahmad, M.A.; Abdullah, A.N.; Othman, M.H.; Hussain, P.; Zainuddin, A. Metal release of
multilayer coatings by physical vapour deposition (PVD). Procedia Eng. 2016, 148, 254–260. [CrossRef]
52. Imbeni, V.; Martini, C.; Lanzoni, E.; Poli, G.; Hutchings, I.M. Tribological behaviour of multi-layered PVD
nitride coatings. Wear 2001, 251, 997–1002. [CrossRef]
53. Wasa, K.; Kitabatake, M.; Adachi, H. Thin Film Materials Technology: Sputtering of Compound Materials; William
Andrew: Amsterdam, The Netherlands, 2004.
54. Decher, G.; Schlenoff, J.B. Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials; Wiley:
Weinheim, Germany, 2003.
55. Silva, F.J.G. Estudo da Estrutura e Comportamento Tribológico de Revestimentos Duros e Ultra-Duros
Executados no Vácuo. Master’s Thesis, FEUP, Porto, Portugal, 2001. (In Portuguese)
56. Bass, R.B.; Lichtenberger, L.T.; Lichtenberger, A.W. Effects of Substrate Preparation on the Stress of Nb Thin
Films. IEEE Trans. Appl. Supercond. 2003, 13, 3298–3300. [CrossRef]
Coatings 2018, 8, 402 20 of 22
57. Karabacak, T.; Senkevich, J.J.; Wang, G.C.; Lu, T.M. Stress reduction in sputter deposited films using
nanostructured compliant layers by high working-gas pressures. J. Vac. Sci. Technol. A 2005, 23, 986–990.
[CrossRef]
58. Estrada-Martínez, J.L.; Banda, J.A.M.; García, U.P.; Muñoz, J.R.; Muñoz, J.L.F.; Lira, M.M.; Ángel, O.Z. Set-up
method on properties of Bax Sr1−x TiO3 thin films deposited by RF-magnetron co-sputtering by projecting
temperature and stoichiometric effect. Preprints 2017, 2017100043. [CrossRef]
59. Plummer, J.D.; Deal, M.; Griffin, P.B. Silicon VLSI Technology: Fundamentals, Practice, and Modeling; Prentice
Hall: Upper Saddle River, NJ, USA, 2000; p. 817.
60. Rother, B.; Ebersbach, G.; Gabriel, H.M. Substrate-rotation systems and productivity of industrial PVD
processes. Surf. Coat. Technol. 1999, 116–119, 694–698. [CrossRef]
61. Martinho, R.P. Revestimentos PVD Mono e Multicamada Para Moldes Utilizados na Injecção de Plásticos
Reforçados. Master’s Thesis, FEUP, Porto, Portugal, 2009. (In Portuguese)
62. Steimann, P.A.; Hintermann, H.E. Adhesion of TiC and Ti(C, N) coatings on steel. J. Vac. Sci. Technol. A 1985,
3, 2394–2400. [CrossRef]
63. Barshilia, H.C.; Ananth, A.; Khan, J.; Srinivas, G. Ar + H2 plasma etching for improved adhesion of PVD
coatings on steel substrates. Vacuum 2012, 86, 1165–1173. [CrossRef]
64. Lente, H.V.; Til, J.I.V. Articulation of sustainability in the emerging field of nanocoatings. J. Clean. Prod. 2008,
16, 967–976. [CrossRef]
65. Gassner, M.; Figueiredo, M.R.; Schalk, N.; Franz, R.; Weiß, C.; Rudigier, H.; Holzschuh, H.; Bürgind, W.;
Pohler, M.; Czettl, C.; Mitterer, C. Energy consumption and material fluxes in hard coating deposition
processes. Surf. Coat. Technol. 2016, 299, 49–55. [CrossRef]
66. Klocke, F.; Döbbeler, B.; Binder, M.; Kramer, N.; Grüter, R.; Lung, D. Ecological evaluation of PVD and CVD
coating systems in metal cutting processes. In Proceedings of the 11th Global Conference on Sustainable
Manufacturing, Berlin, Germany, 23–25 September 2013.
67. Hogmark, S.; Jacobson, S.; Larsson, M. Design and evaluation of tribological coatings. Wear 2000, 246, 20–33.
[CrossRef]
68. Jiang, X.; Yang, F.C.; Chenc, W.C.; Lee, J.W.; Chang, C.L. Effect of nitrogen-argon flow ratio on the
microstructural and mechanical properties of AlSiN thin films prepared by high power impulse magnetron
sputtering. Surf. Coat. Technol. 2017, 320, 138–145. [CrossRef]
69. Li, B.S.; Wang, T.G.; Ding, J.; Cai, Y.; Shi, J.; Zhang, X. Influence of N2 /Ar Flow Ratio on Microstructure and
Properties of the AlCrSiN Coatings Deposited by High-Power Impulse Magnetron Sputtering. Coatings 2018,
8, 3. [CrossRef]
70. Alamia, J.; Bolz, S.; Sarakinos, K. High power pulsed magnetron sputtering: Fundamentals and applications.
J. Alloys Compd. 2009, 483, 530–534. [CrossRef]
71. Rother, B.; Jehn, H.A.; Gabriel, H.M. Multilayer hard coatings by coordinated substrate rotation modes in
industrial PVD deposition systems. Surf. Coat. Technol. 1996, 86–87, 207–211. [CrossRef]
72. Bobzin, K.; Brögelmann, T.; Kalscheuer, C.; Liang, T. High-rate deposition of thick (Cr,Al) ON coatings by
high speed physical vapor deposition. Surf. Coat. Technol. 2017, 322, 152–162. [CrossRef]
73. Liu, M.J.; Zhang, M.; Zhang, Q.; Yang, G.J.; Li, C.X.; Li, C.J. Gaseous material capacity of open plasma jet in
plasma spray-physical vapor deposition process. Appl. Surf. Sci. 2018, 428, 877–884. [CrossRef]
74. Kolzer Vacuum Coating Equipment. Available online: http://www.kolzer.com (accessed on 15 July 2018).
75. CemeCon—The Tool Coating. Available online: http://www.cemecon.de/en (accessed on 15 July 2018).
76. High Performance Coatings for Tools and Components Oerlikon Balzers. Available online: https://www.
oerlikon.com (accessed on 15 July 2018).
77. Teer Coatings. Available online: http://www.teercoatings.co.uk/index.php?page=13 (accessed on 4 October
2018).
78. Panjana, M.; Cekada, M.; Panjan, P.; Zalar, A.; Peterman, T. Sputtering simulation of multilayer coatings in
industrial PVD system with three-fold rotation. Vacuum 2008, 82, 158–161. [CrossRef]
79. Mitterer, C. PVD and CVD hard coatings. In Comprehensive Hard Materials; Sarin, V.K., Ed.; Elsevier:
Amsterdam, The Netherlands, 2014; Volume 2, pp. 449–467. [CrossRef]
80. Linss, V. Comparison of the large-area reactive sputter processes of ZnO: Al and ITO using industrial size
rotatable targets. Surf. Coat. Technol. 2016, 290, 43–57. [CrossRef]
Coatings 2018, 8, 402 21 of 22
81. Linss, V. Challenges in the industrial deposition of transparent conductive oxide materials by reactive
magnetron sputtering from rotatable targets. Thin Solid Films 2017, 634, 149–154. [CrossRef]
82. Rizzo, A.; Valerini, D.; Capodieci, L.; Mirenghi, L.; Benedetto, F.D.; Protopapa, M.L. Reactive bipolar pulsed
dual magnetron sputtering of ZrN films: The effect of duty cycle. Appl. Surf. Sci. 2018, 427, 994–1002.
[CrossRef]
83. Wackelgard, E.; Hultmark, G. Industrially sputtered solar absorber surface. Sol. Energy Mater. Sol. Cells 1998,
54, 165–170. [CrossRef]
84. Rösemann, N.; Ortner, K.; Petersen, J.; Bäke, M.; Bräuer, G.; Rösler, J. Microstructure of gas flow sputtered
thermal barrier coatings: Influence of bias voltage. Surf. Coat. Technol. 2017, 332, 22–29. [CrossRef]
85. Rösemann, N.; Ortner, K.; Petersen, J.; Schadow, T.; Bäker, M.; Bräuer, G.; Rösler, J. Influence of bias voltage
and oxygen flow rate on morphology and crystallographic properties of gas flow sputtered zirconia coatings.
Surf. Coat. Technol. 2015, 276, 668–676. [CrossRef]
86. Weirather, T.; Czettl, C.; Polcik, P.; Kathrein, M.; Mitterer, C. Industrial-scale sputter deposition of Cr1−x Alx N
coatings with 0.21 ≤ x ≤ 0.74 from segmented targets. Surf. Coat. Technol. 2013, 232, 303–310. [CrossRef]
87. Bagcivan, N.; Bobzin, K.; Theiß, S. (Cr1−x Alx )N: A comparison of direct current, middle frequency pulsed
and high power pulsed magnetron sputtering for injection molding components. Thin Solid Films 2013, 528,
180–186. [CrossRef]
88. Anders, A. A review comparing cathodic arcs and high power impulse magnetron sputtering (HiPIMS).
Surf. Coat. Technol. 2014, 257, 308–325. [CrossRef]
89. Gudmundsson, J.T.; Brenning, N.; Lundin, D.; Helmersson, U. High power impulse magnetron sputtering
discharge. J. Vac. Sci. Technol. A 2012, 30, 030801. [CrossRef]
90. Lin, J.L.; Sproul, W.D.; Moore, J.J.; Wu, Z.L.; Lee, S.; Chistyakov, R.; Abraham, B. Recent advances in
modulated pulsed power magnetron sputtering for surface engineering. JOM 2011, 63, 48–58. [CrossRef]
91. Yazdi, M.; Lomello, F.; Wang, J.; Sanchette, F.; Dong, Z.; White, T.; Wouters, Y.; Schuster, F.; Billard, A.
Properties of TiSiN coatings deposited by hybrid HiPIMS and pulsed-DC magnetron co-sputtering. Vacuum
2014, 109, 43–51. [CrossRef]
92. Alami, J.; Maric, Z.; Busch, H.; Klein, F.; Grabowy, U.; Kopnarski, M. Enhanced ionization sputtering: A
concept for superior industrial coatings. Surf. Coat. Technol. 2014, 255, 43–51. [CrossRef]
93. Wu, Z.L.; Li, Y.G.; Wu, B.; Lei, M.K. Effect of microstructure on mechanical and tribological properties of
TiAlSiN nanocomposite coatings deposited by modulated pulsed power magnetron sputtering. Thin Solid
Films 2015, 597, 197–205. [CrossRef]
94. Oliveira, J.C.; Ferreira, F.; Anders, A.; Cavaleiro, A. Reduced atomic shadowing in HiPIMS: Role of the
thermalized metal ions. Appl. Surf. Sci. 2018, 433, 934–944. [CrossRef]
95. Lin, J.; Wei, R. A comparative study of thick TiSiCN nanocomposite coatings deposited by dcMS and HiPIMS
with and without PEMS assistance. Surf. Coat. Technol. 2018, 338, 84–95. [CrossRef]
96. Bandorf, R.; Sittinger, V.; Bräuer, G. High Power Impulse Magnetron Sputtering–HIPIMS. In Comprehensive
Materials Processing, 1st ed.; Hashmi, S., Ed.; Elsevier: Amsterdam, The Netherlands, 2014; pp. 75–99.
[CrossRef]
97. Li, C.; Tian, X.; Gong, C.; Xu, J. The improvement of high power impulse magnetron sputtering performance
by an external unbalanced magnetic field. Vacuum 2016, 133, 98–104. [CrossRef]
98. Li, C.; Tian, X.; Gong, C.; Xu, J.; Liu, S. Synergistic enhancement effect between external electric and magnetic
fields during high power impulse magnetron sputtering discharge. Vacuum 2017, 143, 119–128. [CrossRef]
99. Tiron, V.; Velicu, I.L.; Mihăilă, I.; Popa, G. Deposition rate enhancement in HiPIMS through the control of
magnetic field and pulse configuration. Surf. Coat. Technol. 2018, 337, 484–491. [CrossRef]
100. Ganesan, R.; Akhavan, B.; Dong, X.; McKenzie, D.R.; Bilek, M.M.M. External magnetic field increases both
plasma generation and deposition rate in HiPIMS. Surf. Coat. Technol. 2019, 352, 671–679. [CrossRef]
101. Wu, B.; Haehnlein, I.; Shchelkanov, I.; Lain, J.M.; Patel, D.; Uhlig, J.; Jurczyk, B.; Leng, Y.; Ruzic, D.N. Cu
films prepared by bipolar pulsed high power impulse magnetron sputtering. Vacuum 2018, 150, 216–221.
[CrossRef]
102. Bras, P.; Frisk, C.; Tempez, A.; Niemi, E.; Björkman, C.P.; Brasa, P.; Frisk, C.; Tempez, A.; Niemi, E.;
Platzer-Björkman, C. Ga-grading and Solar Cell Capacitance Simulation of an industrial Cu(In,Ga)Se2 solar
cell produced by an in-line. Vacuum 2017, 636, 367–374. [CrossRef]
Coatings 2018, 8, 402 22 of 22
103. Tapia, E.; Iranzo, A.; Pino, F.; Rosa, F.; Salva, J. Methodology for thermal design of solar tubular reactors
using CFD techniques. Int. J. Hydrog. Energy 2016, 41, 19525–19538. [CrossRef]
104. Abdel-Fattah, A.; Fateen, S.; Moustafa, T.; Fouad, M. Three-dimensional CFD simulation of industrial Claus
reactors. Chem. Eng. Res. Des. 2016, 112, 78–87. [CrossRef]
105. Bouaouina, B.; Mastail, C.; Besnard, A.; Mareus, R.; Nita, F.; Michel, A.; Abadias, G. Nanocolumnar TiN
thin film growth by oblique angle sputter-deposition: Experiments vs. simulations. Mater. Des. 2018, 160,
338–349. [CrossRef]
106. Sliwa, A.; Mikuła, J.; Gołombek, K.; Tanski, T.; Kwasny, W.; Bonek, M.; Brytan, Z. Prediction of the properties
of PVD/CVD coatings with the use of FEM analysis. Appl. Surf. Sci. 2016, 388, 281–287. [CrossRef]
107. Venkateswara Raoa, R. The Significant Application of FEM to Evaluate the Mechanical Properties of Thin
Films. Procedia Mater. Sci. 2014, 6, 1260–1265. [CrossRef]
108. Bouzakis, K.; Skordaris, G.; Klocke, F.; Bouzakis, E. A FEM-based analytical–experimental method for
determining strength properties gradation in coatings after micro-blasting. Surf. Coat. Technol. 2009, 203,
2946–2953. [CrossRef]
109. Prades, L.; Dorado, A.; Climent, J.; Guimerà, X.; Chiva, S.; Gamisans, X. CFD modeling of a fixed-bed biofilm
reactor coupling hydrodynamics and biokinetics. Chem. Eng. J. 2017, 313, 680–692. [CrossRef]
110. Phuan, Y.; Ismail, H.; Garcia-Segura, S.; Chong, M. Design and CFD modelling of the anodic chamber of
a continuous PhotoFuelCell reactor for water treatment. Process Saf. Environ. Prot. 2017, 111, 449–461.
[CrossRef]
111. Adebiyi, D.; Popoola, A.; Botef, I. Experimental Verification of Statistically Optimized Parameters for
Low-Pressure Cold Spray Coating of Titanium. Metals 2016, 6, 135. [CrossRef]
112. Silva, A.; Monteiro, C.; Souza, V.; Ferreira, A.; Jaimes, R.; Fontoura, D.; Nunhez, J. Fluid dynamics and
reaction assessment of diesel oil hydrotreating reactors via CFD. Fuel Process. Technol. 2017, 166, 17–29.
[CrossRef]
113. Sen, S.; Lake, M.; Kroppen, N.; Farber, P.; Wilden, J.; Schaaf, Ç. Self-propagating exothermic reaction analysis
in Ti/Al reactive films using experiments and computational fluid dynamics simulation. Appl. Surf. Sci.
2017, 396, 1490–1498. [CrossRef]
114. Depla, D.; Leroy, W.P. Magnetron sputter deposition as visualized by Monte Carlo modeling. Thin Solid Films
2012, 520, 6337–6354. [CrossRef]
115. Trieschmann, J. Neutral gas simulation on the influence of rotating spokes on gas rare faction in high-power
impulse magnetron sputtering. Contrib. Plasma Phys. 2017, 58, 394–403. [CrossRef]
© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).